Ultra low thermo fusion PVC plastisol coating and textile printing ink

ABSTRACT

The present invention relates to a novel plastisol composition that cures at a temperature much lower than conventional plastisols. Also disclosed is a method of applying the composition.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority under 35 U.S.C. § 119(e) to U.S.Provisional Patent Application Ser. No. 62/344,136, filed on Jun. 1,2016, which is hereby incorporated by reference in its entirety.

FIELD OF THE INVENTION

The present disclosure relates to the field of plastisol, in particular,to a PVC plastisol that cures at temperatures lower than conventionalcompositions.

BACKGROUND OF THE INVENTION

Various existing plastisol are used for a variety of applicationsincluding surface coating for waterproofing, decorating, embellishing,as inks for screen printing designs on substrates such as textiles, forcoating wires, cable and fishing lines, and for creating casts frommolds. Typically, plastisol consists of PVC particles suspended in aliquid plasticizer with various other agents to achieve desiredproperties such as color, particle dispersion, and viscosity. At roomtemperature, they are in a liquid paste state and will not dry byevaporation. When heated to high temperatures of around 177 degreesCelsius (about 350 degrees Fahrenheit), the plastisol will cure and forma flexible permeant solid.

Typically, an automated screen printing press is used for commercialscreen printing. The automated screen printing press consists of aseries of stations arranged in a circle and a series of correspondingpallets. Each station may further consist of either a printing head or aflash cure unit. The pallets rotate along the circle, stopping at eachstation. The printing process begins by manually setting the substrateon a pallet at the first station using a temporary adhesive. Thetemporary adhesive prevents the substrate from shifting and movingduring the printing process. The first plastisol ink is applied to thesubstrate. The pallet rotates to the second station. A flash cure unitcures or gels the ink. The flash cure unit heats the ink to around 177degrees Celsius (about 350 degrees Fahrenheit). The operatingtemperature of the flash cure unit depends on the distance to thesubstrate, the duration of the cure, and the type of plastisol. Flashcures are required for multi-color print on light color and dark colorsubstrates. Specifically, conventional processes have the followinglimitations: (1) Multi-Color Print on light color substrate needs flashcure every three or four print; (2) Multi Color Print on Dark Color(e.g. black, blue, brown, red, purple) substrates needs flash cure afterthe first color (normally, white or grey) print as underlay andthereafter every three or four color print in order to prevent excessiveink absorption into substrate(reducing opacity effect) and ink migrationinto other color or colors, build-up ink on print side of screen andincrease opacity. After the flash cure, sufficient time is required tocool off heated plate, ink and substrate to prevent ink migration,blocking screen by ink build-up, and other problematic issues. This isaccomplished by either rotating two or three plates (stations) withoutprinting process or incorporating a cooling mechanism such as a fan.Once cooled, the next station can apply the second color. The process ofapplying ink, flash curing, and cooling repeats for other ink color orcolors. At final station, the substrate with the completed design printis manually transferred to a conveyor dryer.

The conveyer dryer consists of a conveyer belt and a heating chamber.The product is placed on the conveyer belt and passes through theheating chamber. Referring to FIG. 2, typically, the heating elementtemperature of the electrical conveyer dryer is 540 degrees Celsius(1000 degrees Fahrenheit) to achieve temperatures between 93-170 degreesCelsius (200-340 degrees Fahrenheit) at the surface of the substrate.Alternative, gas-fired vortex belt dryers achieve substrate surfacetemperatures of between 150 and 180 degrees Celsius (300-360 degreesFahrenheit).

The high temperature required to cure and dry PVC plastisol presents anumber of problems well-known in the industry. The heat causes the PVCto release toxic hydrogen chloride gas which poses an occupationalhazard to those working with PVC plastisol. The high temperature alsorequires high energy consumption which places a burden on producers,energy providers, and the environment. The high temperature alsoprecludes the use of heat-sensitive substrates including but not limitedto acrylic, polyester, spandex, nylon, polypropylene, artificialleather, and rubber. Heat-sensitive substrates currently requiresolvent-based compositions which are costlier to manufacture than PVCplastisol, potentially toxic, and contain large volumes of volatileorganic compounds (VOC) which pose environmental risks, includingcontributing to climate change.

In addition, the high temperature increases mechanical stress and causesthe plastisol to deform. It also degrades the adhesives used to keepsubstrates in place during the plastisol ink application. This requiresthe liberal use of expensive and potentially toxic heat-resistantadhesives. The high temperature (higher than water boiling point) alsocauses disperse dye thermo-migration(sublimation) by decomposing dyesand bleed into the plastisol. This permanently discolors the plastisol.To counter this, the plastisol may be made more viscous, which makesworking with the plastisol more difficult. Alternatively, expensivehigh-energy dyes less susceptible to dye sublimation can be used.

The high temperature also requires more cooling between applications andbefore handling. This requires more time and expensive and largeequipment to facilitate cooling including intermediate cooling stationsbetween applications and conveyor belt dryers after final application.

Currently existing methods of producing low-temperature curing PVCplastisol have problems such as short shelf-life which render themcommercially non-viable or require more frequent or longer flash curing.

In addition to the problems associated with high temperature curing,currently available plastisol requires the addition of a bonding agentin order to adhere to some substrates such as hydrophobic andcrystallized substrates. The plastisol with bonding agents have a shortshelf-life and may discolor the plastisol. In addition, currentlyavailable plastisol has a lower surface tension than the substrateswhich can results in poor coverage on the substrates. They are alsobrittle and stiff once cured.

Also, when currently available PVC plastisol-based products are disposedand incinerated, they release the toxic hydrogen chloride gas again.

Therefore, a need exists for an improved and environmentally friendlyPVC plastisol.

SUMMARY OF THE INVENTION

The present invention meets such a need. Described herein is a novelplastisol composition formulated to replace current hazardous and toxicpolyvinyl chloride plastisol by incorporating a unique combination oflow temperature gelling and fusible plasticizers and polymer or polymerswhich will not start the elimination and formation of toxic agent(hydrochloride gas—HCl) from polymer or polymers and is also phthalatefree. The new plastisol composition has a lower curing temperature thanconventional plastisols and superior bonding and leads to densercoverage without de-wetting and crawling, and post-cure durability andwater based ink like soft and thin feel. Further, due to the propertiesof very fast fusion at ultra low temperature, cooling in multicolorapplication would not be necessary, whereas for conventional classic PVCplastisol or other PVC free plastisol cooling down measures after flashcure are unavoidable. Furthermore, the product would not need flash curethermal treatment one after another color deposit or printing. Becauseconvey drier is no longer needed, the curing process for the presentplastisol also saves energy and space. As a result, the plastisol of thepresent invention poses much less health risk and is moreenvironmentally friendly.

The plastisol of the present invention also replaces solvent based andultra-violet curable coating and ink used for coating and printingserigraphic medias and can be used on very thermal heat sensitivematerials such as soft and hard vinyl, polyester, polyurethane (e.g.lycra or spandex), polypropylene woven or non-woven fabric. Carefullyselected ingredients of new invented plastisol decrease crawling problemand deposit interruption and provide a flexible and soft touch feeling,as well as guarantee smooth and very dense deposit. The plastisol thusprovides robust adhesion on every textile substrate without the additionof catalyst or bonding agent.

The plastisol maintain prolonged aged stable and creamy Newtonianviscosity without sharp increase instead of heavy pseudoplasticviscosity during storage period. Further, the plastisol contributes tostatic elimination without induction of moisture and provide very strongresistance to Ultra Violet and harsh weather.

The plastisol composition of the present invention includes:

-   (a) a first copolymer of vinyl chloride and vinyl acetate and    optionally a second copolymer of vinyl chloride and vinyl acetate,    wherein the mean particle size of the second copolymer is at least    about 30% bigger than the mean particle of the first copolymer, and    the ratio by weight between the first copolymer and the second    copolymer ranges from about 4:1 to about 25:1 and-   (b) a plasticizer mixture comprising at least three plasticizers    selected from the group consisting of 2,2,4-trimethyl-1,3    pentanediol diisobutyrate, dioctyl terephthalate, dibutyl    terephthalate, and benzyl butyl 1,2-cyclohexyldicarboxylate.

In some embodiments, the ratio between the total weight of theplasticizers and the total weight of the first and the second copolymersranges from about 5:10 to about 9:10.

In some embodiments, less than about 5% by weight of the first copolymeris derived from vinyl acetate. In some embodiments, the mean particlesize of the first copolymer is less than about 0.075 mm. In someembodiments, the mean particle size of the second copolymer is biggerthan about 0.085 mm.

In some embodiments, the plasticizer mixture comprises2,2,4-trimethyl-1,3 pentanediol diisobutyrate, and the ratio between theweight of the 2,2,4-trimethyl-1,3 pentanediol diisobutyrate and thetotal weight of the first and second copolymers ranges from about 1:200and 1:10 by weight. In some embodiments, the plasticizer mixturecomprises dioctyl terephthalate, and the ratio between the dioctylterephthalate and the total weight of the first and second copolymersranges from about 1:10 and 1:3 by weight. In some embodiments, theplasticizer mixture comprises benzyl butyl 1,2-cyclohexyldicarboxylate,and the ratio between the benzyl butyl 1,2-cyclohexyldicarboxylate andthe total weight of the first and second copolymers ranges from about1:10 and 1:6 by weight. In some embodiments, the plasticizer mixturecomprises dibutyl terephthalate, and the ratio between the dibutylterephthalate and the total weight of the first and second copolymersranges from about 1:4 and 1:2 by weight.

The plastisol composition can further include at least one ingredientselected from the group consisting of a wetting agent, a dispersingagent, a cross-linking agent, a filler, a blowing agent, a rheologymodifier, a thixotropic agent, a lubricant, an anti-static agent, a heatstabilizer, a pigment, a flame retardant, a foaming agent, a viscosityreducer, a dilatancy reducer, and an UV absorber.

In some embodiments, the wetting agent and/or dispersing agent isselected from the group consisting of an alkoxylate, a polar acidicester, an anionic electrolyte, an acidic polyether,polydimethylsiloxane, a fluoro-substituted polyacrylate, and anycombination thereof. In some embodiments, the crosslinking agent isselected from the group consisting of a peroxide, a tri-acrylate, andany combination thereof. In some embodiments, the filler is selectedfrom the group consisting of calcium carbonate, alumina thrihydrate,micro sphere, silica, nepheline syenite, and any combination thereof. Insome embodiments, the blowing agent is selected from the groupconsisting of an expandable microsphere, a copolymer of acrylate, and acombination thereof. In some embodiments, the rheology modifier and/or athixotropic agent is silica. In some embodiments, the lubricant isselected from the group consisting of paraffin wax,polytetrafluoroethlene, and a combination thereof. In some embodiments,the anti-static agent is selected from the group consisting of an alkoxytitanate, an ammonium salt, and a combination thereof.

Another aspect of the invention provides a method of using the plastisolcomposition including (a) applying the plastisol composition to asubstrate; and (b) exposing plastisol composition to a UV or heat sourceto cure the composition.

In some embodiments, the plastisol composition is exposed to the heatsource at a temperature ranging from about 80° C. to about 115° C. Insome embodiments, the plastisol composition is exposed to the heatsource at a temperature of lower than about 120° C. In some embodiments,the plastisol composition is exposed to the heat source for less thanabout 10 seconds. In some embodiments, the plastisol composition isexposed to the heat source for less than about 5 seconds. In someembodiments, the substrate comprises a material selected from polyester,polyethylene, acrylic, polypropylene, natural or synthetic leather,polyamide, cotton, and any combination thereof. In some embodiments, thesubstrate is a textile substrate and the plastisol composition isprinted on the substrate. In some embodiments, one or more additionalplastisol compositions are printed on the substrate prior to step (b).

A related aspect provides a product manufactured according to the methoddescribed herein, wherein the product includes for example, printedtextile (e.g. garment and cover) and coated substrates (e.g. tubing andauto parts).

These and other aspects of the present invention will be described ingreater detail below.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows description of printing processes of dark color substratewith plastisol ink with automatic printing machine (16 heads and 18pallets) under low cure temperature for six or seven color printing

DETAILED DESCRIPTION OF THE INVENTION

Various embodiments of the present invention provide a novel plastisolcomposition which overcome the drawbacks of traditional ink. Theadvantages lie in the improved product quality and durability as well asreduced production cost. In particular, the printing processsignificantly cut down energy consumption and the generation ofhazardous waste. A wide range of materials are suitable substrates forprinting the composition of the present invention.

While the following text may reference or exemplify specific componentsof a composition or a method of utilizing the composition, it is notintended to limit the scope of the invention to such particularreferences or examples. Various modifications may be made by thoseskilled in the art, in view of practical and economic considerations,such as the weight percentage of a plasticizer and the temperature tocure the composition.

The articles “a” and “an” as used herein refers to “one or more” or “atleast one,” unless otherwise indicated. That is, reference to anyelement or component of the present invention by the indefinite article“a” or “an” does not exclude the possibility that more than one elementor component is present.

The term “about” as used herein refers to the referenced numericindication plus or minus 10% of that referenced numeric indication. Forexample, the term “about” appears in the description of percentageweights of plasticizers because the weights are only approximations andwill vary depending upon the specific compositions and the applicationthereof. Even though the limits that define the present weightpercentage of the plasticizers may be approximate, selecting a valuewithin these ranges will enable one skilled in plastisol formulation toprepare of desirable viscosity plastisols with a minimum ofexperimentation.

The term “plastisol” as used herein refers to a liquid polymercomposition comprising a particulate form of a polymer dispersed in aliquid phase comprising a plasticizer for the polymer. The presentinvention is not restricted to any particular polymer, although theinvention may be described in terms of vinyl chloride polymers. Theplastisol can include at least one non-crosslinked polymer.

The term “substantially free” means that a substance (e.g. phthalateplasticizer) is non-present in a plastisol composition, or the amount ofthe substance is so small that it does not impact the properties of theplastisol composition.

An aspect of the invention provides a plastisol composition whichincludes a first copolymer vinyl chloride and vinyl acetate and aplasticizer mixture containing 3 or more plasticizers. The combinationof the multiple plasticizers is critical for curing at a low temperatureand enhancing the tensile strength and the flexibility of the cured inkfilm. In addition, the cured ink film controls fiber fibrillation verywell. There is a smooth and dense uniform layer on every substrateincluding for example untreated cotton garments.

Plasticizer

Plasticizers provide versatility to PVC and are key ingredients andtools for the vinyl formulator. They are used to adjust hardness (orsoftness), impart stain resistance, alter tensile properties (such asstrength, elongation or flexibility) and processability as required fora multitude of applications, including without limitation flexible vinylapplications. While hundreds of plasticizers have been produced, only afew remain having acceptable performance properties when combined withvinyl or other polymeric materials. In some embodiments, theplasticizers of the plastisol described herein are substantially free ofphthalates.

Plasticizers serve as a vehicle for the dispersion of resin (polymer)particles, such as PVC. The dispersion is initially a two-phase,heterogeneous system. Use of plasticizers in polymeric dispersionspromotes the formation of homogeneous systems and polymer fusion occursupon heating. The higher the solvating power, the lower the temperatureat which a homogeneous system is fused, which, in turn, decreases theresidence time and increases the speed at which polymeric compositionscan be processed into an end product, resulting in a faster, moreefficient and economical process.

In further examples, the intended function of the plasticizer in thefully gelled, plasticized polyvinyl chloride preparation is not only toprovide the desired softness but also to have maximum resistance tomigration into adjacent media. Further demands placed upon plasticizersresult from the desire to avoid hazards to humans and the environment.It is no longer permissible in many countries to use the plasticizersdi(2-ethylhexyl)phthalate, dibutyl phthalate and benzyl butyl phthalatein toys or baby items, or to use the plasticizers diisononyl phthalate,diisodecyl phthalate and di-n-octyl phthalate in toys or baby itemswhich might enter children's mouths. There is therefore a particularrequirement for suitable replacement materials for the abovementionedplasticizers di-(2-ethylhexyl) phthalate, dibutyl phthalate and benzylbutyl phthalate.

In view of these desirable function and the restrictions associated withplasticizers, it is important to adopt a generalized approach ofminimizing or avoiding all phthalate-containing plasticizers in theproduction of plasticized polymers. The result of this is a requirementfor phthalate-free plasticizers or new plasticizer combination which interms of processability and service properties achieve the performancelevel of phthalate-containing plasticizers.

A combination or mixture of 2,2,4-trimethyl-1,3 pentanedioldiisobutyrate, benzyl butyl 1,2-cyclohexyldicarboxylate, and one or moredialkyl terephthalates has been found to be important to a desirablegelling condition and an optimized product profile in terms of a lowfusion/cure temperature, reduced fiber extrusion, improved tensilestrength and other properties. One or more additional plasticizer can beincluded in the combination to further modify the manufacturingcondition and the product profile. The ratio by weight between eachindividual plasticizer in the combination and the first polymer rangesfrom about 1:2 to about 1:25. Exemplary ratios include about 1:3, 1:4,1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:15 and 1:20.

Each of the alkyl group in the dialkyl terephthalate can beindependently a liner or branched and substituted or unsubstitutedC1-C15 alkyl group, such as methyl, ethyl, propyl, butyl, isobutyl,pentyl, isopentyl, hexyl, heptyl, octyl, and isomers and analogsthereof. Examples include dibutyl terephthalate and dioctylterephthalate.

The plasticizers can be prepared according to chemistry procedure knownin the field or can be obtained from a commercial source. For example,the preparation of a dialkyl terephthalate is within the skills of oneof ordinary skill in the art through coupling reactions between adibenzoic acid and an alcohol. Plasticizers such as TXIB, Santicizer278, Santicizer 375, Platinum P-1400, Effusion, Platinum P-1700, andPolysorb are also available from comerical sources.

In further examples, the plasticizer combination includes a dibenzoatesuch as DEGDB, DPGDB, and 1,2-propylene glycol dibenzoate (PGDB). Otherexamples include monobenzoates (derived from benzoic acid and amonohydric alcohol such as 2-ethylhexanol, isooctanol or isononanol),monobenzoates of diols, glycols and ethers of glycols containing from 2to 8 or more carbon atoms, and commercially available esters of diols,such as the mono- and diisobutyrates of 2,2,4-trimethyl-1,3-pentanediol.

Various compounds are suitable substitute for phthalates. As theplasticizer, straight-chain dibasic acid esters can be used such as adioctyl adipate (DOA), a dioctyl azelate (DOZ), and a dioctyl sebacate(DOS). As the plasticizer, phosphoric acid ester series may be used suchas a tricresyl phosphate (TCP), a trioctyl phosphate (TOF), a trixylenylphosphate (TXP), a monooctyl diphenyl phosphate, and amonobutyl-dixylenyl phosphate (B-Z-X). As the plasticizer, benzoic acidester series can be used such as tri(2-ethylhexyl) trimellitate (TOTM),a tri-n-octyl trimellitate, a triisodecyl trimellitate, a tri-iso-octyltrimellitate. As the plasticizer, esters can be used such as a tributylcitrate ester, a trioctyl-acetyl citric acid ester, a trimellitic acidester, a citric acid ester, a sebacic acid ester, an azelaic acid ester,a tri- or tetraethylene glycol ester of maleate C₆-C₁₀ fatty acid, analkyl sulfonic acid ester, and a methyl acetyl ricinoleate. Theplasticizer may be an saturated fatty acid glyceride such as a soybeanoil having double bonds thyereof epoxidized with a hydrogen peroxide ora peracetic acid, that is, en epoxidized soy bean oil (ESBO), too. Theplasticizer may be an epoxidized vegetable oil such as an epoxy compoundof an alkyl oleate ester or the like of butyl or octyl, or a viscous lowpolymerization degree polyester of an average molecular weight of about500 to 8000 having a straight chain of propylene glycol ester units of adibasic acid such as an adipic acid (e.g. an adipic acid polyester, aphthalic acid-based polyester) or the like, too. As the plasticizer, oneof them may be used alone or two or more of them may be used inappropriate combination. In some embodiments, the plastisol compositiondoes not contain a phthalate as a plasticizer.

In some embodiment, the plasticizer combination contains a phthalate asa plasticizer. Among them, the phthalic ester is one of the most commonplasticizers and is easy to be procured, thereby contributing to costreduction. Moreover, the phthalic ester is capable of dispersing thevinyl chloride resin still more uniformly, thereby forming a stablevinyl chloride plastisol. Particularly, from the viewpoint ofelimination of an environmental load, ease of handling, solubility,coating property, storage stability and so on, the diisononyl phthalate(DINP) or the dioctyl phthalate (DOP) is used most commonly among thephthalates.

In some embodiments, the plasticizer combination includes2,2,4-trimethyl-1,3 pentanediol diisobutyrate, dioctyl terephthalate,dibutyl terephthalate, and benzyl butyl 1,2-cyclohexyldicarboxylate. Insome embodiments, the plasticizer combination includes2,2,4-trimethyl-1,3 pentanediol diisobutyrate, dioctyl terephthalate,dibutyl terephthalate, benzyl butyl 1,2-cyclohexyldicarboxylate,1,2-benzenedicarboxylic acid-1,2-benzenedicarboxylicacid-2,2-dimethyl-1-(1-methylethyl)-3-(2-methyl-1-oxoropoxy)propylphenylmethyl ester, and one, two or more commercial plasticizersselected from Santicizer 375, Santicizer 278, platinun p-1700, andpolysorb (isosorbide-biobased plasticizer: e.g. Polysorb ID 46). In someembodiments, the plasticizer combination includes 2,2,4-trimethyl-1,3pentanediol diisobutyrate, dioctyl terephthalate, dibutyl terephthalate,benzyl butyl 1,2-cyclohexyldicarboxylate, 1,2-benzenedicarboxylicacid-1,2-benzenedicarboxylicacid-2,2-dimethyl-1-(1-methylethyl)-3-(2-methyl-1-oxoropoxy)propylphenylmethyl ester (commercially available as Santicizer 278), andPolysorb ID 46 (isosorbide-biobased plasticizer, manufactured byRoquette).

The above described plasticizers can be used individually and in blendswith other plasticizers in applications that include but are not limitedto: adhesives, caulks, architectural coatings, industrial coatings, OEMcoatings, other types of plastisols, sealants, overprint varnishes,polishes, inks, melt compounded vinyl, polysulfides, polyurethanes,epoxies, styrenated acrylics and combinations thereof. Otherapplications will be evident to one skilled in the art based upon thedisclosure herein.

Polymer

Any of the known polymers that can be formulated into a plastisol can beused to prepare low viscosity plastisols in accordance with the presentinvention. The polymers constituting the dispersed phase of the presentplastisols include polymers of ethylenically unsaturated organicmonomers and mixtures of these monomers that can be prepared by a freeradical-initiated emulsion polymerization. Suitable monomers include butare not limited to 1) ethylenically unsaturated halocarbons such asvinyl chloride, 2) ethylenically unsaturated acids such as acrylic andmethacrylic acids and esters thereof with alcohols containing up toeight or more carbon atoms, and 3) copolymers of vinyl alcohol witholefins such as ethylene and vinyl acetate.

As the vinyl monomer to be copolymerized with the vinyl chloride or thevinylidene chloride, there may be used vinyl esters such as a vinylacetate, a vinyl propionate or a vinyl stearate, vinyl ethers such as avinyl methyl ether or a vinyl isobutyl ether, maleic acid esters such asa diethyl maleate or the like, fumaric acid esters such as a dibutylfumarate, (meth)acrylic acid alkyl esters such as a methyl acrylate, anethyl acrylate, a 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate,hydroxyalkyl esters of acrylic acid or methacrylic acid such as2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, a hydroxypropylacrylate, a hydroxypropyl methacrylate, hydroxyalkyl amides of acrylicacid or methacrylic acid such as a N-methylol acrylamide, a N-methylolmethacrylamide, a N-hydroxyethyl acrylamide, a N-dihydroxyethylmethacrylamide, an acrylonitrile or the like. They may be copolymerizedwith the vinyl chloride generally at a rate of less than about 40%, lessthan about 30%, less than about 20%, less than about 10%, or less thanabout 5% by weight (wt %). Among them, the vinyl acetate is preferred asthe monomer to be copolymerized with the vinyl chloride or vinylidenechloride, from the viewpoint of a swelling/gelling property to aplasticizer or a high adhesion to a metal surface. Moreover, the rate ofthe vinyl acetate to be copolymerized is preferably less than about 10%,less than about 5% or less than about 3% from the viewpoint of thestorage stability, water resistance, chemical resistance and the like.The vinyl chloride may also be a crosslinkable copolymer having asuitable crosslinking group. Furthermore, as such vinyl chloride resin,one kind of vinyl chloride resin may be used alone, or two or more kindsof vinyl chloride resins may be used in appropriate combination.

The vinyl chloride resin preferably has an average degree ofpolymerization in the range of 500 to 2500, more preferably in the rangeof 850 to 2000, and still more preferably in the range of 1000 to 1900,from the viewpoint of obtaining a high storage stability, a goodchipping resistance and a tough coating property.

In some embodiments, the first copolymer of vinyl chloride and vinylacetate has a mean particle size of less than about 0.075 mm. Otherexemplary mean particle sizes for the first copolymer include less thanabout 0.070 mm, less than about 0.065 mm, less than about 0.060 mm, lessthan about 0.055 mm, less than about 0.050 mm, less than about 0.045 mm,and less than about 0.045 mm. Vinyl acetate contributes to about 1%,about 2%, about 3%, about 4%, about 5% or about 6% of the copolymer. Thecopolymer can be prepared according to the requirements of the targetcomposition or obtained from a commercial source (e.g. Vinnolit PA5470/5).

The first copolymer can be used in combination with a second polymer.The second copolymer has a bigger mean particle size than the firstcopolymer and provides a number of advantages including reducedviscosity, optimized bonding and mechanical performance of the product,and regulated surface gloss.

The mean particle size or diameter of the second copolymer is at leastabout 35%, at least about 30%, at least about 25%, at least about 20%,at least about 15%, or at least about 10% bigger than the mean particlesize or diameter of the first copolymer. The ratio by weight between thefirst copolymer and the second copolymer ranges from about 70:30 toabout 99:1. Other exemplary ratios by weight between the first copolymerand the second copolymer include about 75:25, about 80:20, about 85:15,about 90:10, and about 95:5. Further examples of the ratio by weightbetween the first copolymer and the second copolymer include from about4:1 to about 35:1, from about 5:1 to about 25:1, from about 5:1 to about20:1, from about 5:1 to about 10:1, and from about 3:1 to about 4:1.

In some embodiments, the second polymer is a copolymer of vinyl chlorideand vinyl acetate. In some embodiments, the second copolymer has a meanparticle size of bigger than about 0.060 mm, bigger than about 0.065 mm,bigger than about 0.070 mm, bigger than about 0.075 mm, bigger thanabout 0.080 mm 0.085 mm, bigger than about 0.090 mm or bigger than about0.100 mm.

Each of the copolymer can have a functional group for cross-linking.Exemplary groups include epoxy group, amino group, hydroxyl and carboxygroup.

Other Components/Ingredients

The plastisol composition can include at least one ingredient selectedfrom a wetting agent, a dispersing agent, a cross-linking agent, afiller, a blowing agent, a rheology modifier, a thixotropic agent, alubricant, an anti-static agent, a heat stabilizer, a pigment, a flameretardant, a foaming agent, a viscosity reducer, a dilatancy reducer,and an UV absorber.

The wetting agent can serves the role such as reducing liquid surfacetension, minimizing foaming, improving colorant acceptance, facilitatingink transfer, and improving ink adhesion. Each of the wetting agentgenerally account for about 0.1% to about 5% of the plastisolcomposition and is often available from a commercial source. Forexample, commercially available Hydropalat WE 3650 (modifiedalkoxylate), CoatOSil 1211 (organomodified polydimethylsiloxane) orAfcona 3700 (fluoro-substituted polyacrylic polymer) can be used as awetting agent and surface tension modifier.

The dispersing agent serves to prevent flocculation of particles byadsorbing on the solid-liquid interface and assuring repulsion betweenthe particles. Examples of dispersing agents include polar acidic ester,anionic electrolyte, acidic polyether, oragno-phosphate compound,polydimethylsiloxane, and a fluoro-substituted polyacrylate.Commercially available dispersing agents include, for example,Disperplast 1142, Disperplast 1150, BYK 1161, Dispex AA 4144, and EFKAFA 4620. Each of the dispersing agent is from about 0.1% to about 5%, orfrom about 1% to about 3% of the plastisol composition and can be usedalone or in combination.

The selection of a cross-linking agent depends on the functional groupof the polymer. For example, acidic phosphates, triazines, polyamines,polyamides and the like are used when the polymer particles have anepoxy group as a functional group; polycaboxylates, polyepoxides and thelike are used when the polymer particles have an amino group as afunctional group. On the other hand, polyisocyanate compounds are usedwhen the polymer particles have a hydroxyl group as a functional group;and polyamides, polyamines, polyepoxides and the like are used when thepolymer particles have a carboxyl group as a functional group. Furtherexamples include 1,1-di(tert-amylperoxy)cyclohexane andtrimethylolpropane triacrylate. Various agents are commerciallyavailable such as TRIGONOX 122-C80 and LUPEROX 531M180. Each of theagents can be used alone or in combination and the amount of each agentis about 1% to about 5% of the polymer by weight.

A filler can serve multiple functions such as reducing the usage oftitanium dioxide or plasticizer, maintaining a desirable viscosity andincreasing opacity. Exemplary fillers include precipitated calciumcarbonate, calcium carbonate, calcium carbide such as precipitatedcalcium carbide, or ultrafine calcium carbide; magnesium carbide;silicates such as silica, talc, diatomaceous earth, clay, and mica;alumina such as alumina trihydrate; expanded micro sphere; glass sphere;microcrystalline silica; and nepheline syenite (about 5-15 microns), andany combination thereof. The fillers can be used alone or in combinationwith each other and each is about 0.1% to about 45%, about 1% to about40%, about 1% to about 35%, about 1% to about 30%, about 5% to about20%, about 5% to about 15%, or about 5% to about 10% of the entireplastisol composition. In some embodiments, each of the fillers is about1% to about 50%, about 1% to about 40%, about 1% to about 35%, about 1%to about 30%, about 1% to about 20%, about 1% to about 10%, about 5% toabout 20%, about 5% to about 15%, or about 5% to about 10% of theplastisol base consisting of plasticizers, wetting & disperse agent, andpolymer or polymers.

A blowing/foaming agent is capable of producing a cellular structure viaa foaming process in a material such as a polymer that undergo hardeningor phase transition. The cellular structure in a matrix can reducedensity, increasing thermal and acoustic insulation. The agent can be aphysical or a chemical agent or a combination of both types of agents.Inorganic agents include sodium borate, and sodium hydrogen carbonate,and organic agents include azodicarboxamide,P,P′-oxybis(benzenesulfonylhydrazide), andN,N′-dinitroso-N,N′-dimethyleterephthalamide. In some additionalembodiments, the blowing agent includes a thermal expandable microsphereand/or a polymer. The polymer can be a single or copolymer of any two orthree of acrylonitrile, methacrylonitrile and methyl methacrylate (e.g,a copolymer particle of about 15 to about 25 microns. Each individualcomponent of the blowing agent is about 0.2% to about 5% of theplastisol composition by weight. The agent can be commercially availablesuch as MS-140 DS and Expancel 031DU.

A rheology agent and/or a thixotropic agent serves to improve uniformedfilm monolayer, prevent undesirable flow, and reduce sedimentation.Silica such as treated or untreated fumed silica and pyrogenic silicaare suitable agents for such purpose. The amount of the agent isgenerally about 0.1% to about 1% of the plastisol composition by weight.

A lubricant can help with reducing heat build-up during manufacturingprocess and preventing gelling during printing. Examples includepolytetrafluoroethlene and crystalline parafinwax. The amount of theagent is generally about 1% to about 5% of the plastisol composition byweight. Commercial agents include SST-4D with about mean particle sizeof about 3 microns.

The use of an anti-static agent prevent or diminish surface electricityby reducing the surface resistivity. In addition, it can reduce moirephenomenon and prevent interruption of smooth and uniformed layerdeposit. The amount of the agent is generally about 1% to about 5% ofthe plastisol composition by weight. Examples include neoalkoxy titanateand dodecylethyldimethylammonium ethyl sulphate. Commercial agentsinclude KS N-100 and EFKA 6780.

An emulsifier can also be used in the plastisol composition. Examples ofthe emulsifier include alkyl sulfate salts such as sodium lauryl sulfateand sodium myristyl sulfate; alkylaryl sulfonate salts such as sodiumdodecylbenzenesulfonate, and potassium dodecylbenzenesullfonate;sulfosuccinate salts such as sodium dioctyl sulfosuccinate, sodiumdihexyl sulfosuccinate; fatty acid salts such as ammonium laurate, andpotassium stearate; anionic surfactants such as polyoxyethylene alkylsulfate salts, and polyoxyethylene alkylaryl sulfate salts; sorbitanesters such as sorbitan monooleate, and polyoxyethylene sorbitanmonostearate; monionic surfactants such as polyoxyethylene alkyl ethers,and polyoxyethylene alkylphenyl ethers; cationic surfactants such ascetylpyridinium chloride, and cetyltrimethylammonium bromide; as well asstyrene/maleic acid copolymer ammonium slat; and the like. an emulsifiermay be used singly, or used in combination with two or more emulsifiers.

These emulsifiers may be used singly, or two or more of them may be usedin combination. The amount of the emulsifier may be usually 0.05 to 5parts by weight, preferably 0.2 to 4.0 parts by weight, per 100 parts byweight of the monomer used.

As the viscosity modifier, there can be cited, for example, solventssuch as xylene, solvent naphtha, mineral spirit, methyl isobutyl ketone,and butyl acetate, and suitable surfactants. Additional agents forreducing viscosity and/or dilatancy include 1-dodecene and carboxylicacid derivatives, which are commercially available such as Viscobyk 4015and 5025. The agent weighs about 1-10% of the weight of the polymer.

Thermal stabilizers are optional as the cure temperature issignificantly reduced. Examples of the thermal stabilizer include metalsoaps such as magnesium stearate, aluminum stearate, calcium stearate,barium stearate, zinc stearate, calcium laurate, barium laurate, andzinc alurte; organotin compounds such as dibutyltin dilaurate,dibutyltin dimaleate, and monobutyltin mercaptide; phosphorous acidesters such as diethyl phosphite, dibutyl phosphite, dioctyl phosphite,diphenyl isodecyl phosphite, tricresyl phosphite, triphenyl phosphite,tris(nonylphenyl) phosphite, and triisooctyl phosphite; and the like.

Pigments are chosen for stability and color-fastness on the substrate tobe imaged. Pigments are particulate in form, which is a consideration onproper dispersion of such solids in the plastisol compositions of thepresent invention. Therefore, some care should be taken to provideadequate mixing of the ingredients of the plastisol ink composition.Pigments are as varied as the colors of desired by the consumer.Pigments are well known to those of skill in the art, and are notdifferent from pigments useful in the plastisol ink compositionscontaining polyvinyl halides and phthalates.

Application of Plastisol Composition

Although the exemplified application illustrate printing the plastisolcomposition on apparels, the present invention is certainly not limitedto such application. the plastisol composition can be applied to variousfields including for example plastisol coating, molding, tubing,thermoforming, flooring covering, rust prevention coating, construction,anti-tripping, rust preventing, medical products, cable insulation &coating, textile decorating and ink printing, serigraphic ink printing,and consumable products. The substrate where the plastisol compositionis applied includes for example, synthetic leather, wall paper, waterproof sheet, floor tile, floor carpet backing, floor cushion, buildingmaterials, roofing tile, guttering, window frame, automotive air & oilfilter, car seat, blood bag & intravenous line, feeding tube, parts ofdialysis, apparels, tarpauline and stretch wrap, food container, bottle,hoses, curtains and many other woven or nonwoven, textile or natural orsynthetic materials. The materials can be made from for examplepolyester, soft vinyl material substrate, acrylic, polypropylenenon-woven, artificial leather, nylon (polyamide), cotton and anycombination thereof.

In addition to printing applications on textiles such as cotton,acrylic, polyester, Spandex (Lycra) and nylon, printing is also possibleon polypropylene, soft and hard PVC, artificial leather, rubber, etc.More specific applications include plastisol coating and molding,calendaring, glove and tool dipping, textile, natural and syntheticleather coating and toy-slash molding. In the flooring coveringindustries, the non-PVC plastisol can be applied to floor tile, floorcarpet backing and floor cushions. For sheets and coverings, the non-PVCplastisol could be applied to synthetic leather, wall paper and sheetsfor water proofing. Applications are also available for buildingmaterials, roofing tile, guttering and window frames. Rust prevention isalso possible by using the non-PVC plastisol for coating. In theautomotive industry, the non-PVC plastisol could be applied to underbody coating for anti-tripping, rust prevention and splash noisedumping, as a sealing compound, spot welding, air and oil filters, carseats, etc. The non-PVC plastisol could also be used for medicalproducts in applications for blood bags and IV tubing. Otherapplications include cable insulation and coating, textile decoratingand printing ink for children's wear, garments, t-shirts, pajamas,underwear at the like. Applications in serigraphic printing ink andpacking materials such as tarpauline, stretch wrap, food containers,bottles and the like are also available. The PVC alternative plastisolprovides superb resistance of disperse dye thermo-migration phenomenon(dye bleeding caused by dye sublimation) for disperse dye dyed man-madesubstrates. It minimizes the effect from bleeding by maintaining fusiontemperature much lower than normal starting temperature.

Due to the properties of very fast fusion at low temperature, heatcooling down steps in multicolor application would not be necessary asin conventional classic PVC Plastisol or other PVC free plastisol, whereheat cooling down measures are unavoidable after flash cure.Furthermore, this product would not need flash cure thermal treatmentone after another color deposit or printing.

The method of using plastisol composition of the present inventiongenerally involves applying the composition to a substrate and allowsthe composition to cure at a suitable temperature within a reasonableperiod of time. The means of application depends on the intended filedof use and the specific substrate. Exemplary approaches include screenprinting, molding, and dipping. More specific methods include forexample extrusion, calendaring, injection molding, rotational molding,dip molding, slush molding, coating, textile printing.

The temperature for curing the plastisol composition can vary dependingon factors such as the components and the target use of the composition.In some embodiments, the cure temperature ranges from about 50° C. toabout 300° C., from about 50° C. to about 250° C., from about 50° C. toabout 200° C., from about 50° C. to about 150° C., from about 50° C. toabout 100° C., from about 60° C. to about 100° C., from about 60° C. toabout 90° C., from about 60° C. to about 95° C., from about 75° C. toabout 250° C., from about 75° C. to about 200° C., from about 75° C. toabout 150° C., from about 75° C. to about 100° C., from about 85° C. toabout 100° C., from about 80° C. to about 115° C., from about 82° C. toabout 115° C., from about 85° C. to about 150° C., from about 85° C. toabout 200° C., from about 85° C. to about 150° C., from about 85° C. toabout 100° C., from about 100° C. to about 300° C., from about 100° C.to about 250° C., from about 100° C. to about 200° C., from about 100°C. to about 150° C., from about 150° C. to about 300° C., from about150° C. to about 250° C., from about 150° C. to about 200° C., fromabout 200° C. to about 300° C., from about 200° C. to about 250° C.,from about 250° C. to about 300° C., from about 30° C. to about 50° C.In further exemplary embodiments, the cure temperature is lower thanabout 500° C., lower than about 450° C., lower than about 400° C., lowerthan about 350° C., lower than about 300° C., lower than about 250° C.,lower than about 200° C., lower than about 150° C., lower than about115° C., lower than about 100° C., lower than about 90° C., lower thanabout 80° C., lower than about 70° C., lower than about 60° C., lowerthan about 50° C., or lower than room temperature. Heating, IR and UVradiation can also be used individually or in combination, at the sametime or sequentially for curing a composition. Unless otherwisespecified, the cure temperature is measured at the surface of theplastisol composition applied to the substrate. The temperature achievedat such surface determines the curing result.

The length of time for curing can vary depending on the specificcomposition, the substrate, and other relevant factors. Exemplarylengths of time include less than about 100 seconds, less than about 80seconds, less than about 60 seconds, less than about 50 seconds, lessthan about 40 seconds, less than about 30 seconds, less than about 20seconds, less than about 15 seconds, less than about 10 seconds, lessthan about 8 seconds, less than about 6 seconds, less than about 4seconds, less than about 3 seconds, and less than about 2 seconds. Insome further embodiments, the time for curing takes about 1, about 2,about 3, about 4, about 5, about 6, about 7, about 8, about 9, about 10,about 15, about 20, about 25, about 30, about 40 seconds. In someexemplary embodiments, the cure condition requires heating at about80°-115° C. for about 10 to about 30 seconds. In some embodiment, thecuring requires heating at about 450° C. for about 3 to about 5 seconds.In some exemplary embodiments, the cure condition requires heating at atemperature of lower than about 100° C. for less than about 10 seconds.In some embodiment, the curing requires heating at about 450° C. forabout 3 to about 5 seconds. In some embodiments of curing, the appliedplastisol composition is exposed to the heat source at a temperatureranging from about 80° C. to about 115° C. for less than about 10seconds or less than about 5 seconds. In some embodiments of curing, theapplied plastisol composition is exposed to the heat source at atemperature lower than about 115° C. for less than about 10 seconds orless than about 5 seconds.

A composition can be cured in a single stage or over multiple stages.Multiple plastisol compositions with the same or different colors can beapplied to a substrate at the same time or sequentially. In someembodiments, two, three, four, five, six, seven, eight, nine, ten ormore compositions are applied sequentially or at the same time to asubstrate before the compositions are being subject to a curingcondition (e.g. flash heating). Therefore, the cooling step betweencuring individual compositions is not necessary in the presentinvention.

EXAMPLES Example 1

A PVC plastisols was blended in dual shaft disperser or triple shaftdisperser at room temperature or 16° C. for approximately 15-35 minutesusing following procedure: the liquid additives were dispersed in thecombination of plasticizers, then the polymers and extender wereintroduced and mixed for 5-10 min and then the solid and other liquidadditives were mixed. The mixing was continued for 5-10 min. Therheology modifier was then added and the blending continued for 5minutes.

When a plasticizer or plasticizers, a polymers, and a filler werecombined in blending mixer, heat started to build up due to friction ofcomponents to about 32° C. or higher. The elated temperature andmechanical stress could accelerate plastisol gelation and affect theirmechanical properties, dimensional stability and other properties (e.g.viscosity, printability, processability, and aged stable shelf life).Therefore, in order to minimizing heat build-up of plastisol compound,appropriate measures and equipment should be adopted such as using waterjacketed double wall mixing tank, or adding polymer into the plasticizeror plasticizers at same time. Alternatively, by adding the polymer firstor using less plasticizer, heat buildup can be kept under control.

The composition of a plastisol is illustrated as follows:

A. plasticizers - non-phthalate polymer modifiers 1 dioctylterephthalate (e.g Eastman 168) 20-60% of polymer^(a) 2. dibutylterephthalate (e.g Eastman Effusion) 20-60% of polymer^(a) 3. benzylbutyl 1,2-cyclohexyldicarboxylate 10-30% of polymer^(a) 4.1,2-benzenedicarboxylic acid-1,2-benzenedicarboxylic 5-20% ofpolymer^(a) acid-2,2-dimethyl-1-(1-methylethyl)-3-(2-methyl-1-oxoropoxy)propyl phenylmethyl ester) (total weight of plasticizer 1, 2,3 and 4 is 60-80% of polymer) B. coupling agent 0.1-0.6% of polymer^(a)C. wetting agent 0.1-2% of TFM^(b) D. disperse agent 0.1-2% of TFM^(b)E. crosslinking & coupling-agent 0.1-4% of polymer^(a) F. deaerator0.1-1% of TFM^(b) G. prepared pigment toners 1-40% of TFM^(b) H.filler - precipitated calcium carbonate 5-40% of Base^(d) I. blowingagent copolymer/isobutane 0.5-3% of TFM^(b) J. heat stabilizer 1 to 3%of polymer^(a) K. flexbilizer non-caboxylated butadiene acrylonitrile0.5-1% of TFM^(b) copolymer latex L. polyvinyl chloride polymers 1.homopolymers VINNOLIT E70TT 10-100 parts 2. homopolymer VINNOLIT EP 606010-50 parts 3. suspension homopolymer: VINNOLIT C 65C or C65W 10-20parts 4. copolymer VINNOLIT PA 5470/5 10-100 parts (Total parts ofsingle use or combination of the above 4 polymers: 100 parts)^(c) M.rheology modifier 5-10% of polymer^(a) N. anti-static agent 1-5% ofTFM^(b) ^(a)the percentage value refers to the weight of the individualplasticizer relative to the weight of the polymer(s); ^(b)the percentagevalue refers to the weight of the individual agent relative to the totalformulation weight (TFM) of the plastisol composition; ^(c)the totalamount of the polymer or polymers is about 10-70% of the totalformulation weight (TFM) of the plastisol composition; ^(d)The Baseconsists of the plasticizers, the wetting agent, the dispersing agent,coupling agent, and the polymer(s).

Example 2

Using procedures similar to those in Example 1, a second plastisolcomposition includes the following components:

A. plasticizers - non-phthalate polymer modifiers 1. dioctylterephthalate (e.g. eastman 168) 30-60% of polymer^(a) 2. dibutylterephthalate (e.g. eastman effusion) 30-60% of polymer^(a) 3. benzylbutyl 1,2-cyclohexyldicarboxylate 10-30% of polymer 4. plasticizer(platinum p-1700) 30-50% of polymer^(a) (total weight of plasticizer 1,2, 3 and 4 is 60-80% of polymer) B. wetting agent hydropalat we 36500.1-2% of TFM^(b) C. dispersing agent efka 4670 0.1-2% of TFM^(b) D.crosslinking & co-agent trigonox 122-c80 0.1-4% polymer^(a) E. defoamerefka pb 2744 0.1-1% TFM^(b) F. prepared pigment toners 5-15% of TFM^(b)G. filler - precipitated calcium carbonate socal s-322 0-50% of base^(d)H blowing agent copolymer/isobutane expancel 031DU 0.5-3% of TFM^(b) I.heat stabiizer plas-check 775 1 to 3% of polymer^(a) J. flexibizernon-caboxylated butadience acrylonitrile 0.5-1% of TFM^(b) copolymer.latex (nychem 1552) K. polymers 1. homopolymer vinnolit E70 TTt 10-50parts 2. homopolymer vinnolit EP 6060. 10-50 parts 3. suspensionhomopolymer: vinnolit c65c or c65w 10-20 parts 4. copolymer vinnolit pa5470/5 10-100 parts (Total parts of single use or combination of theabove 4 polymers: 100 parts)^(c) L. rheology modifier santicizer 3755-10% of polymer^(a) M. anti-static 1-5% of TFM^(b) ^(a)the percentagevalue refers to the weight of the individual plasticizer relative to theweight of the polymer(s); ^(b)the percentage value refers to the weightof the individual agent relative to the total formulation weight (TFM)of the plastisol composition; ^(c)the total amount of the polymer orpolymers is about 20-70% of the total formulation weight (TFM) of theplastisol composition; ^(d)The base consists of the plasticizers, thewetting agent, the dispersing agent, coupling agent, and the polymer(s).

Example 3

The printing process of dark color substrate with the plastisolcomposition of the present invention is illustrated in FIG. 1. Theprinting machine has 16 heads and 18 plates and is capable of printing 6or 7 colors. The plates are positioned around the center of the printingmachine and labeled as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,15, 16, 17, and 18.

The plates serves the following roles: the first plate was used toinfeed T-shirt; the second plate was used to print white underlay; thethird plate was used for flash cure unit (at a temperature of betweenabout 150° C. to 205° C.); the forth plate was optionally used for thesecond color printing; the fifth plate was used for the third colorprinting; the six plate was used for the forth color printing; theseventh plate was used for flash unit (at a temperature of between about150° C. to 205° C.); the eighth plate was optionally used for coolingmeasure of heated plate; the ninth plate was used for the fifth colorprinting; the tenth plate was used for the sixth color printing; theeleventh plate was used for the seventh color printing; the twelfthplate was used for final flash cure unit (at a temperature of betweenabout 200° C. to 250° C. for about 4 seconds) for complete fusion; thethirteenth plate was not used, or used for outfeed; the fourteenth platewas not used; the fifteenth plate was not used; the sixteen plate wasnot used; the seventeens plate was not used; the eighteenth plate wasused to outfeed printed T-Shirt.

After the above steps, no additional curing or fusion process wasnecessary. Two or three designs can be printed with one equipment sametime and impression per hour can be increased up to 1500.

It should be noted that any one of plates 12, 13, 14, 15 16, 17 and 18can be used for outfeed. For example, in the event Plate 12 is used foroutfeed, one or more of Plate 13, 14, 15, and 16 can be used to print asecond design, plate 17 can be used for flash unit for final cure, andplate 18 can be used for outfeed for the second design print.

With the process described herein, electrically powered and/or gas firedconveyor fusion system is no longer necessary. With the elimination ofconveyor thermo-fusion system, the consumption of energy and emission ofgas waste can drastically cut down. Further, expensive hot flashadhesive is no longer necessary.

It will be understood by those of skill in the art that numerous andvarious modifications can be made without departing from the spirit ofthe present invention. Therefore, it should be understood that thevarious embodiments of the present invention described herein areillustrative only and not intended to limit the scope of the presentinvention.

The invention claimed is:
 1. A plastisol composition comprising: (a) afirst copolymer of vinyl chloride and vinyl acetate and optionally asecond copolymer of vinyl chloride and vinyl acetate, wherein the secondcopolymer has a mean particle size that is at least about 30% biggerthan the mean particle size of the first copolymer, and the ratio byweight between the first copolymer and the second copolymer ranges fromabout 4:1 to about 25:1 and (b) a plasticizer mixture comprising dioctylterephthalate, dibutyl terephthalate, 2,2,4-trimethyl-1,3 pentanedioldiisobutyrate and benzyl butyl 1,2-cyclohexyldicarboxylate, wherein theratio between the weight of the 2,2,4-trimethyl-1,3 pentanedioldiisobutyrate and the total weight of the first and second copolymersranges from about 1:200 to 1:10.
 2. The plastisol composition of claim1, wherein less than about 5% by weight of the first copolymer isderived from vinyl acetate.
 3. The plastisol composition of claim 1,which comprises both the first copolymer and the second copolymer. 4.The plastisol composition of claim 1, wherein the mean particle size ofthe first copolymer is less than about 0.075 mm.
 5. The plastisolcomposition of claim 1, wherein the mean particle size of the secondcopolymer is bigger than about 0.085 mm.
 6. The plastisol composition ofclaim 1, wherein the ratio between the total weight of the plasticizersand the total weight of the first and the second copolymers range fromabout 5:10 to about 9:10.
 7. The plastisol composition of claim 1,wherein the ratio between the weight of the dioctyl terephthalate andthe total weight of the first and second copolymers ranges from about1:10 to 1:3.
 8. The plastisol composition of claim 1, wherein the ratiobetween the weight of the benzyl butyl 1,2-cyclohexyldicarboxylate andthe total weight of the first and second copolymers ranges from about1:10 to 1:6.
 9. The plastisol composition of claim 1, wherein the ratiobetween the weight of the dibutyl terephthalate and the total weight ofthe first and second copolymers ranges from about 1:4 to 1:2.
 10. Theplastisol composition of claim 1, further comprising at least oneingredient selected from the group consisting of a wetting agent, adispersing agent, a cross-linking agent, a filler, a blowing agent, arheology modifier, a thixotropic agent, a lubricant, an anti-staticagent, a heat stabilizer, a pigment, a flame retardant, a foaming agent,a viscosity reducer, a dilatancy reducer, and an UV absorber.
 11. Theplastisol composition of claim 10, wherein the wetting agent and/ordispersing agent is selected from the group consisting of an alkoxylate,a polar acidic ester, an anionic electrolyte, an acidic polyether,polydimethylsiloxane, a fluoro-substituted polyacrylate, and anycombination thereof.
 12. The plastisol composition of claim 10, whereinthe crosslinking agent is selected from the group consisting of aperoxide, a tri-acrylate, and any combination thereof.
 13. The plastisolcomposition of claim 10, wherein the filler is selected from the groupconsisting of calcium carbonate, alumina trihydrate, micro sphere,silica, nepheline syenite, and any combination thereof.
 14. Theplastisol composition of claim 10, wherein the blowing agent is selectedfrom the group consisting of an expandable microsphere, a copolymer ofacrylate, and a combination thereof.
 15. The plastisol composition ofclaim 10, wherein the rheology modifier and/or a thixotropic agent issilica.
 16. The plastisol composition of claim 10, wherein the lubricantis selected from the group consisting of paraffin wax,polytetrafluoroethlene, and a combination thereof.
 17. The plastisolcomposition of claim 10, wherein the anti-static agent is selected fromthe group consisting of an alkoxy titanate, an ammonium salt, and acombination thereof.
 18. The plastisol composition of claim 1, which issubstantially free from phthalate plasticizer.
 19. The plastisolcomposition of claim 1, which is configured for being printed on atextile substrate.
 20. A method of printing or coating the plastisolcomposition of claim 1 on a substrate, comprising: (a) applying theplastisol composition to a substrate; and (b) exposing plastisolcomposition to a UV or heat source to cure the composition.
 21. Themethod of claim 20, wherein the plastisol composition is exposed to theheat source at a temperature of lower than about 115° C.
 22. The methodof claim 20, wherein the plastisol composition is exposed to the heatsource at a temperature ranging from about 80° C. to about 115° C. 23.The method of claim 20, wherein the plastisol composition is exposed tothe heat source for less than about 10 seconds.
 24. The method of claim20, wherein the plastisol composition is exposed to the heat source forless than about 5 seconds.
 25. The method of claim 20, wherein thesubstrate comprises a material selected from polyester, polyethylene,acrylic, polypropylene, natural or synthetic leather, polyamide, cotton,and any combination thereof.
 26. The method of claim 20, wherein thesubstrate is a textile substrate and the plastisol composition isprinted on the substrate.
 27. The method of claim 20, wherein one ormore additional plastisol compositions are printed on the substrateprior to step (b).